Herbicidal Compositions

ABSTRACT

The present invention provides an improved herbicidal composition including (a) an effective amount of an herbicidal cyclohexandione oxime compound or agriculturally acceptable salt thereof; (b) one or more esters of a fatty acid; (c) a salt of dodecylbenzensulfonic acid; (d) at least one nonionic surfactant selected from the group consisting of polyoxyethylene plant oils and polyoxyethylene sorbitan esters; and (e) optionally another herbicide.

This application is a continuation of U.S. patent application Ser. No.10/974,711, filed on Oct. 28, 2004.

FIELD OF THE INVENTION

The present invention relates to herbicidal compositions. Moreparticularly, the present invention relates to improvedadjuvant-containing formulations suitable as postemergent herbicideswhich improve the efficacy of herbicides.

BACKGROUND OF THE INVENTION

It is known that herbicidal compositions containing cyclohexanedioneoxime compounds such as clethodim, sethoxydim, alloxydim, cycloxydim,butroxydim, tralkoxydim, tepraloxydim, and profoxydim are difficult toformulate, since the active ingredients are sensitive to chemicalinstability. Many adjuvant materials, surfactants, and even water, forexample, can lead to significant chemical degradation. Because chemicalstability is commercially desirable, as well as required by theEnvironmental Protection Agency, it is common in the agriculturalchemical industry to formulate cyclohexanedione oxime compounds with anemphasis on chemical stability and good mixing characteristics, ratherthan on optimization of herbicidal efficacy.

Current graminicides typically require the addition of oil-basedadjuvants (known as “crop oil concentrates”) in order to achievecommercially acceptable stability and weed control. In particular,herbicidal efficacy for cyclohexanedione oxime compounds requires addingcrop oil concentrates at the time of application in the grower fields.Rather than having to prepare a tank mix from separate herbicide andcrop oil containers, it would be commercially desirable to prepareherbicides and crop oils in one formulation which is ready to dilute.However, because crop oil concentrates commonly used in the marketplaceare recommended at the use rate of 16 to 32 fluid ounces per acre, ithas not been practical to provide cyclohexanedione oxime compounds andcrop oil concentrates as premixed, ready to dilute formulations.

Ready to dilute adjuvant-containing post-emergent herbicidalformulations are described in U.S. Pat. No. 5,084,087. The formulationcomprises a mixture of one or more herbicidal compounds, apolyoxyalkylene nonionic surfactant having a hydrophilic-lipophilicbalance (HLB) of from 10 to about 14, an anionic surfactant selectedfrom the group consisting of the dialkyl metal sulfosuccinates and themetal alkylbenzene sulfonates, optionally a low foaming polyoxyalkylenenonionic surfactant having an HLB of less than 10, and a lower alkanolester of a long chain fatty acid. This patent does not describe orsuggest the particular herbicidal composition of the present invention,including the surfactant component and advantageous properties describedherein.

SUMMARY OF THE INVENTION

An object of the present invention is to provide improved herbicidalcompositions and methods of use which exhibit excellent herbicidalefficacy and chemical stability. These and other objects and advantagesof the present invention have been achieved by providing an herbicidalcomposition comprising (a) an effective amount of an herbicidalcyclohexanedione oxime compound or agriculturally acceptable saltthereof; (b) one or more esters of a fatty acid; (c) a salt ofdodecylbenzenesulfonic acid; and (d) at least one nonionic surfactantselected from the group consisting of polyoxyethylene plant oils andpolyoxyethylene sorbitan esters. As an additional, optional, component,an aromatic hydrocarbon solvent may be used.

In a preferred embodiment, the present invention provides an herbicidalcomposition comprising (a) about 1 to 40% by weight of the herbicidalcyclohexanedione oxime compound or agriculturally acceptable saltthereof; (b) about 10 to 90% by weight of the one or more esters of afatty acid; (c) about 0.1 to 5% by weight of the salt ofdodecylbenzenesulfonic acid; and (d) about 0.2 to 12% by weight of theat least one nonionic surfactant mentioned above.

In a second preferred embodiment, the present invention provides anherbicidal composition comprising (a) about 1 to 40% by weight of theherbicidal cyclohexanedione oxime compound or agriculturally acceptablesalt thereof; (b) about 10 to 75% by weight of the one or more esters ofa fatty acid; (c) about 0.1 to 5% by weight of the salt ofdodecylbenzenesulfonic acid; (d) about 0.2 to 12% by weight of the atleast one nonionic surfactant mentioned above; and (e) about 10 to 90%by weight of the aromatic hydrocarbon solvent.

In a more preferred embodiment, the present invention provides anherbicidal composition comprising (a) 10 to 30% by weight of clethodim;(b) 20 to 50% by weight of a mixture of the methyl esters of C16-C18fatty acids; (c) 1 to 5% by weight of polyoxyethylene castor oil and/orpolyoxyethylene sorbitan monotallate; (d) 0.5 to 3% by weight of calciumdodecylbenzenesulfonate; and (e) 10 to 60% by weight of the aromatichydrocarbon solvent.

In a further embodiment, the present invention provides a method forcontrolling the growth of vegetation, comprising applying to thevegetation an effective amount of the herbicidal composition describedabove.

DETAILED DESCRIPTION OF THE INVENTION

The herbicidal compositions of the present invention offer severaladvantages, including, for example, one or more of the following: theyare chemically stable formulations, they do not require the addition ofa crop oil concentrate, they provide superior control of susceptibleweed species, provide increased speed of herbicide absorption andherbicide symptoms, they result in increased speed of glyphosateabsorption, and they can be tank mixed with other herbicides without adecrease in weed control.

The herbicidal ingredient of the present invention is an herbicidalcompound having a cyclohexanedione oxime structure. Certaincyclohexanedione oximes are known in the art as having excellentherbicidal activity against a variety of post-emergent grasses in avariety of environments. Typical examples include clethodim, sethoxydim,alloxydim, cycloxydim, butroxydim, tralkoxydim, tepraloxydim, andprofoxydim. Cyclohexanedione oximes can be obtained on the market. Forexample, clethodim is provided by Valent U.S.A. Corporation or ArvestaCorporation, sethoxydim and alloxydim are provided by Nippon SodaCompany or BASF Corporation, cycloxydim and profoxydim are provided byBASF Corporation, and butroxydim is provided by CropCare Australasia.Alloxydim is usually provided as its sodium salt. Preferredcyclohexanedione oximes are clethodim and sethoxydim. Most preferred isclethodim. The active ingredient can be employed in several technicalforms such as Clethodim Technical (Valent U.S.A. Corporation or ArvestaCorporation), which comprises 95.3% clethodim by weight and 4.7% inertingredients, and a 70% or 37% Manufacturing Use Product which is asolution of Clethodim Technical in aromatic solvent. For any of thecyclohexanedione oxime compounds which have an optically active center,such as clethodim, both racemic and enantiomeric forms may be used asdesired.

The content of the herbicidal cyclohexanedione oxime compound in theherbicidal composition is preferably about 1% to 40% by weight, morepreferably 3% to 30% by weight, and most preferably 10% to 30% byweight.

The esters of a fatty acid are preferably C1-C8 alkyl (e.g. methyl,ethyl, isopropyl, butyl, isobutyl, octyl) esters of a fatty acid. Thefatty acids can be saturated or unsaturated organic monobasic acids suchas palmitic acid, myristic acid, stearic acid, lauric acid or oleicacid. The carbon numbers of the fatty acids are preferably 12 to 22.Typical non-limiting examples include methyl oleate, methyl palmitate,isopropyl myristate, octyllaurate, isopropyl palmitate, and butylstearate. The preferred esters of a fatty acid are a mixture comprisedpredominantly of the methyl esters of C16-C18 fatty acids.

The C16-C18 fatty acid methyl ester mixture used in the herbicidalformulations tested in the examples set forth herein was CE-1618 (C1623-32%, C18 65-75%, primarily methyl oleate), available from Proctor andGamble. Other suitable esters of fatty acids include but are not limitedto CE-1695, CE-1897, SE-1885, also available from Proctor and Gamble;AGNIQUE® ME and AE products, available from Cognis Corporation; STEPANC-65 and C-68 and KESSCO® IPP, IPM and BS, available from StepanCompany; and PRIOLUBE® 1530 and 1400, available from Uniqema.

The content of the esters of a fatty acid in the herbicidal compositionis preferably about 10% to 90% by weight, more preferably 20% to 70% byweight, most preferably 20% to 50% by weight.

The ratio of the esters of a fatty acid to the herbicidal ingredient ispreferably 0.5:1 to 25:1, more preferably 0.8:1 to 12:1, and mostpreferably 1:1 to 4:1.

The salt of dodecylbenzenesulfonic (DDBS) acid is preferably a salt thatcan work as an anionic surfactant, and typically is a calcium, sodium,potassium, or amine salt. The preferred salt is calcium DDBS.

[18] The calcium DDBS used in the herbicidal formulations tested in theExamples set forth herein was WITCONATE® P-1220EH (60% CaDDBS, 15%propylene glycol, and 25% 2-ethylhexanol), available from Akzo Nobel.Other suitable salts of DDBS include but are not limited to WITCONATE® P1860, P 5020 B, P 1020 B, and P 1060 B, also available from Akzo Nobel;AGNIQUE® ABS products, available from Cognis Corporation; NINATE® 401-A,available from Stepan Company; and RHODACAL® 60BE, 60BHF and 70B,available from Rhodia.

The content of the salt of DDBS acid in the herbicidal composition ispreferably about 0.1% to 5% by weight, more preferably 0.5% to 5% byweight, and most preferably 0.5% to 3% by weight.

The nonionic surfactant is selected from the group consisting ofpolyoxyethylene (POE) plant oils and POE sorbitari esters. The POE plantoils may be hydrogenated. Examples of the plant oils include but are notlimited to castor oil, rapeseed oil and linseed oil. The HLB of thepolyoxyethylene plant oil is preferably 14.4-18.0. A preferred POE plantoil is POE (54 moles ethylene oxide (EO)) castor oil (POE (54) castoroil), which has an HLB of 14.4.

The POE (54) castor oil used in the herbicidal formulations tested inthe Examples set forth herein was EMULPON® CO-550, available from AkzoNobel. Other suitable polyoxyethylene plant oils include but are notlimited to AGNIQUE® CSO, SBO and RSO products, available from CognisCorporation; and ALKAMULS® OR-40 and EL-719, available from Rhodia.

The POE sorbitan esters of the present invention are preferably theethoxylated sorbitan esters of fatty acids. The fatty acid may bederived from animal or vegetable sources. The definition of the fattyacid is as described above. Typical examples include but are not limitedto POE sorbitan monotallate, POE sorbitan monooleate, POE sorbitantrioleate, POE sorbitan monostearate, POE sorbitan tristearate, POEsorbitan monomyristate, and POE sorbitan monolaurate. The HLB of the POEsorbitan ester is preferably 14.4-18.0. A preferred POE sorbitan esteris POE (30 moles EO) sorbitan monotallate (POE(30) sorbitanmonotallate), which has a HLB of 15.4.

The POE (30) sorbitan monotallate used in the herbicidal formulationstested in the Examples set forth herein was ARMOTAN® AL 69-66, availablefrom Akzo Nobel. Other suitable POE sorbitan esters include but are notlimited to ARMOTAN® SMO 20, also available from Akzo Nobel; AGNIQUE®SML, SMS, STS, and SMO products, available from Cognis Corporation;TOXIMUL® SEE-340 and 341, available from Stepan Company, and ALTOX® 80and 8916TF, TWEEN® 20, 40, and 60, available from Uniqema.

The content of the nonionic surfactant in the herbicidal composition ispreferably about 0.2% to 12% by weight, more preferably 0.5% to 8% byweight, and most preferably 1% to 5% by weight.

The optional aromatic hydrocarbon solvent is not restricted so long asit can dissolve the herbicidal cyclohexanedione oxime compound. Aromatichydrocarbon solvents are readily available from a number of sources.Examples include but are not limited to xylene; phenylxylylethane;HISOLO SAS-296 (a mixture of 1-phenyl-1-xylylethane and1-phenyl-1-ethylphenylethane), available from Nippon Petroleum Company;CACTUS SOLVENT® HP-DMN (containing 80% of dimethylnaphthalene) andCACTUS SOLVENT® P-100 (alkylbenzene having carbon number of 9 to 10),available from Nikko Petrochemical Company; SOLVESSO™ 100 and AROMATIC100, AROMATIC 150 and SOLVESSO™ 150, SOLVESSO™ 200 and AROMATIC 200(aromatic hydrocarbons), available from ExxonMobil Chemical; and HI-SOL®10 and HI-SOL® 15 (aromatic hydrocarbons), available from AshlandChemical Company.

[26] Preferred aromatic hydrocarbon solvents are AROMATIC 150 andSOLVESSO™ 150, and HI-SOL® 15. AROMATIC 150 was used in the herbicidalformulations tested in the Examples set forth herein.

[27] The content of the aromatic hydrocarbon solvent in the herbicidalcomposition is preferably up to about 90% by weight, more preferably 10%to 75% by weight, and most preferably 10% to 60% by weight.

Further, the herbicidal composition optionally comprises anothersolvent, and/or auxiliary components such as antioxidant (e.g., propylgallate, ascorbyi palmitate, butylated hydroxy toluene, or butylatedhydroxyanisole), thickener, antifoaming agent, perfume and dyestuff.

Examples of other solvents include but are not limited to2-ethylhexanol, propylene glycol, ethylene glycol, diethylene glycol,and glycerin. When 2-ethylhexanol or propylene glycol is used, thecontent of the additional solvent in the herbicidal composition ispreferably about 0.5% to 4% by weight.

[30] In the herbicidal formulations tested in the Examples set forthherein, small amounts of 2-ethylhexanol and propylene glycol werecarried over from the source of the salt of DDBS acid (WITCONATE®P-1220EH (60% CaDDBS, 15% propylene glycol, and 25% 2-ethylhexanol),available from Akzo Nobel).

When the antioxidant propyl gallate is used, the content of the propylgallate in the herbicidal composition is preferably about 0.01% to 1% byweight, more preferably 0.05% to 0.5% by weight. Preferred embodimentsof the herbicidal composition of the present invention include 0.25%propyl gallate by weight.

The herbicidal composition of the present invention can be prepared bymixing (a) an herbicidal cyclohexanedione oxime compound oragriculturally acceptable salt thereof as an herbicidal ingredient, (b)one or more esters of a fatty acid, (c) a salt of DDBS acid, (d) atleast one nonionic surfactant selected from the group consisting of POEplant oils and POE sorbitan esters and (e) optionally an aromatichydrocarbon solvent, and optionally other solvents, auxiliaries and soon. There are no specific mixing condition requirements, and thecomponents do not need to be added in any particular order. However,when an antioxidant such as propyl gallate is used, it may be desirableto premix the antioxidant with the nonionic surfactant(s) or with amixture of the nonionic surfactant(s), the salt of DDBS acid, and theone or more esters of a fatty acid.

The herbicidal compositions of the present invention are typicallyutilized as emulsifiable concentrates, namely they are diluted withwater to give an emulsion and applied to weeds, especially graminaceousweeds such as barnyardgrass (Echinochloa crus-galli), green foxtail(Setaria viridis), giant foxtail (Setaria fa beri), large crabgrass(Digitaria sanguinalis), annual bluegrass (Poa annua), blackgrass(Alopecurus myosuroides), oats (Avena sativa), wild oats (Avena fatua),johnsongrass (Sorghum halepense), quackgrass (Agropyron repens), downybrome (Bromus tectorum), and bermudagrass (Cynodon dactylon), inbroad-leaf crop (e.g. soybean, cotton, sugarbeet, peanut, alfalfa,potatoes, flax, canola, sunflowers, fruiting vegetables, legume crops,cranberries, cucurbit crops, head and stem brassica crops, leafybrassica crops, lettuce crops, mustard seed, onion, garlic, shallots,leaks, root vegetables, rhubarb, spinach, strawberry, sweet potato, andmany other crops) fields.

The application dosage is generally about 0.063 to 0.250 pounds activeingredient per acre (about 70 to 280 grams of active ingredient perhectare) in the amount of the herbicidal cyclohexanedione oximecompound. One of ordinary skill in the art could determine anappropriate application dosage, which may vary with crop, objectiveweeds, weather conditions and so on. The dilution of the herbicidalcomposition can be used for aerial application by helicopter, plane orradio-controlled helicopter.

One of the advantages of the herbicidal composition of the presentinvention is its ability to achieve commercially acceptable weed control(>90%) without the need for tank mixing with crop oil concentrates, cropoil concentrate blends, nonionic surfactant adjuvants, or ammoniumsulfate. However, in certain circumstances, these materials may bedesirable to increase efficacy, or may be required by a tank-mixpartner. For example, glyphosate formulations commonly require theaddition of ammonium sulfate. Examples of crop oil concentrates, cropoil concentrate blends, or nonionic surfactant adjuvants that can beused with the present invention include AGRI-DEX®, DYNE-AMIC®, andINDUCE®, available from Helena Chemical Corporation; SILWET® L-77,available from Loveland Industries; PRIME OIL® and PRIME OIL® EV,DESTINY®, and PREFERENCE®, manufactured by Agriliance; HERBIMAX® andMSO® CONCENTRATE, manufactured by Loveland Industries; BRITZ O/S BLEND,manufactured by Britz Fertilizers, Incorporated; and MORACT®,manufactured by Wilbur-Ellis.

In addition, under practical conditions it can be desirable to mixherbicides to achieve a broader spectrum of weed control, for example toprevent the need to make two separate applications of individualherbicides, such as one to control grass weeds and a second to controlbroadleaf weeds. However, mixing herbicides can be problematic if thereis antagonism between the active ingredients, between the formulations,or between the adjuvant recommendations. The present invention overcomesthose limitations with respect to glyphosate formulations, and also withrespect to other herbicides such as but not limited to CADRE® (activeingredient imazapic, available from BASF Corporation), STORM™ (activeingredients acifluorfen and bentazon, available from United Phosphorus,Incorporated), and COBRA® (active ingredient lactofen, available fromValent U.S.A. Corporation).

Examples

To illustrate the invention, specific examples are set forth below.These examples are merely illustrations and are not to be understood aslimiting the scope and underlying principles of the invention in anyway. Various modifications of the invention in addition to those shownand described herein will become apparent to those skilled in the artfrom the following examples and foregoing description. Suchmodifications are also intended to fall within the scope of the appendedclaims.

In the following examples, herbicidal formulations of the presentinvention are tested for their efficacy against a variety of commonweeds. In many cases, comparisons are made to similar commerciallyavailable herbicidal formulations which contain clethodim as the activeingredient. One such commercially available herbicidal formulation usedfor comparison purposes is PRISM® 1 EC, a product of Valent U.S.A.Corporation. Another commercially available herbicidal formulation usedfor comparison purposes is SELECT® 2 EC, also a product of Valent U.S.A.Corporation.

In all the tables showing efficacy of the herbicidal formulationsagainst various species of weeds, the numerical values represent thepercentage of weed control, or percent kill of the various species. Theuse rate of the herbicidal formulations is expressed in terms of poundsof active ingredient per acre (lb ai/A).

Several herbicidal formulations of the present invention were tested inthe following examples. These herbicidal formulations are defined asfollows:

Formulation A % by weight Clethodim Technical 13.2 C16-C18 fatty acidmethyl esters 35.3 Ca DDBS 1.5 POE(54) castor oil 1.2 POE(30) sorbitanmonotallate 1.0 Propyl gallate 0.2 2-Ethylhexanol 0.6 Propylene glycol0.4 AROMATIC 150 balance

Formulation B % by weight Clethodim Technical 21.4 C16-C18 fatty acidmethyl esters 26.5 Ca DDBS 1.1 POE(54) castor oil 0.9 POE(30) sorbitanmonotallate 0.8 Propyl gallate 0.2 2-Ethylhexanol 0.5 Propylene glycol0.3 AROMATIC 150 balance

Formulation C % by weight Clethodim Technical 3.5 C16-C18 fatty acidmethyl esters 70.6 Ca DDBS 3.0 POE(54) castor oil 2.3 POE(30) sorbitanmonotallate 2.1 Propyl gallate 0.2 2-Ethylhexanol 1.2 Propylene glycol0.7 AROMATIC 150 balance

Formulation D % by weight Clethodim Technical 7.0 C16-C18 fatty acidmethyl esters 70.6 Ca DDBS 3.0 POE(54) castor oil 2.3 POE(30) sorbitanmonotallate 2.1 Propyl gallate 0.2 2-Ethylhexanol 1.2 Propylene glycol0.7 AROMATIC 150 balance

Formulation E % by weight Clethodim Technical 24.9 C16-C18 fatty acidmethyl esters 22.1 Ca DDBS 0.9 POE(54) castor oil 0.7 POE(30) sorbitanmonotallate 0.6 Propyl gallate 0.2 2-Ethylhexanol 0.4 Propylene glycol0.2 AROMATIC 150 balance

Formulation F % by weight Clethodim Technical 14.1 C16-C18 fatty acidmethyl esters 35.4 Ca DDBS 1.5 POE(54) castor oil 1.2 POE(30) sorbitanmonotallate 1.0 Propyl gallate 0.3 2-Ethylhexanol 0.6 Propylene glycol0.4 AROMATIC 150 balance

Formulation G % by weight Clethodim Technical 25.5 C16-C18 fatty acidmethyl esters 24.9 Ca DDBS 1.1 POE(54) castor oil 0.8 POE(30) sorbitanmonotallate 0.7 Propyl gallate 0.2 2-Ethylhexanol 0.4 Propylene glycol0.3 AROMATIC 150 balance

Formulation H % by weight Clethodim Technical 26.4 C16-C18 fatty acidmethyl esters 30.4 Ca DDBS 1.3 POE(54) castor oil 1.0 POE(30) sorbitanmonotallate 0.9 Propyl gallate 0.0 2-Ethylhexanol 0.5 Propylene glycol0.3 AROMATIC 150 balance

Formulation I (example of formulation not according to the presentinvention) % by weight Clethodim Technical 28.6 C16-C18 fatty acidmethyl esters balance TOXIMUL ® TAAS 5* 1.8 TRYLOX ® 5900** 0.9 TRYLOX ®5907*** 0.3 Propyl gallate 0.5 *ethoxylated tallow amine ether sulfate,available from Stepan Company **POE(5) castor oil, HLB 4.9, availablefrom Cognis Corporation ***POE(36) castor oil, HLB 12.6, available fromCognis Corporation

Example 1

The speed of herbicide absorption was compared. The results in Table Ishow that the various herbicidal formulations of the present inventionresult in more rapid herbicide absorption in ROUNDUP READY® corn, whencompared to the commercial PRISM®1 EC formulation for clethodim.

Materials & Methods-General Application: ROUNDUP READY® corn was used inthis example as the target weed species. Applications were made toactively growing corn which had reached 12-18 inches in height. Allherbicide treatments were made using identical equipment and applicationmethods.

Materials & Methods—Measuring Speed of Herbicide Absorption: Theherbicide active ingredient in Formulation A (and related formulationsB, C, D) and PRISM® is clethodim. It is known in public literature thatclethodim acts in susceptible plants as a meristematic inhibitor. At thegrowth stage that these corn plants were treated, the meristematicregion of the plant is imbedded inside the main stem tissue (in otherwords it is not exposed for direct chemical application). With theresearch methods used in this experiment the only known way theherbicide active ingredient could reach the meristem resulting in plantmortality is absorption through the leaf surface and subsequenttranslocation to the meristematic region.

In this example, all above ground leaf tissue was removed from the cornplants after treatment application (tissue was cut off and removed fromthe plant). This plant harvest technique occurred 30, 60 and 120 minutesafter treatment application. Since absorption and translocation had tooccur while the plant still had sprayed leaf tissue intact, plantcontrol or plant mortality only occurred in those treatments wherebyspeed of absorption was complete within the time frame prior to plantharvest.

Results & Discussion: At 7 days after treatment (DA T) the treatmentscontaining no added adjuvant (i.e., NIS, COC or AMS) had herbicidesymptoms ranging from 0 to 93% control. Detailed data are contained inthe following table:

TABLE I % Control of RR Corn 7-DAT at 3 Use Rate Different Plant HarvestIntervals. Product ID (lb ai/a) 30 minutes 60 minutes 120 minutes*Untreated — 0 0 0 Formulation A 0.075 30 27 42 Formulation B 0.075 10 3053 Formulation C 0.075 7 30 93 Formulation D 0.075 27 37 82 Prism 0.0750 10 27 *At the 120 minute plant harvest interval all experimentalclethodim formulations had numerically higher % RR corn control than didthe commercial standard formulation Prism, indicating an increased speedof herbicide absorption as a function of these new experimentalformulations. Formulation C had 93% control at the 120 minute plantharvest interval compared to 27% for Prism.

Significance: The enhanced clethodim formulations of the presentinvention are superior to PRISM® 1 EC due to increased speed ofherbicide absorption, resulting in more rapid herbicide symptoms insusceptible weed species. The herbicide active ingredient clethodim ischemically unstable when exposed to UV radiation (i.e., intensesunlight). Therefore the longer the chemical resides on the outside ofthe leaf surface after application the more subject the herbicide is todegradation into non-herbicidal forms. A formulation that allows forquicker plant absorption will avoid this UV degradation problem andcould possibly result in less active ingredient needed to control theundesired weed species.

Example 2

The speed of herbicide absorption was compared for herbicidalformulations with added ammonium sulfate. Ammonium sulfate is commonlyused and often required as a tank mix adjuvant with glyphosate toincrease efficacy. The results in Table II show that the herbicidalformulations of the present invention result in more rapid herbicideabsorption in ROUNDUP READY® corn, when compared to PRISM® 1 EC, whenammonium sulfate is added to the herbicidal formulations.

Materials & Methods—General Application: ROUNDUP READY® corn was used inthis example as the target weed species. Applications were made toactively growing corn which had reached 12-18 inches in height. Allherbicide treatments included ammonium sulfate at 2.5 lbs per acre andwere made using identical equipment and application methods.

Materials & Methods—Measuring Speed of Herbicide Absorption: Theherbicide active ingredient in Formulation A (and related formulationsB, C, D) and PRISM® is clethodim. It is known in public literature thatclethodim acts in susceptible plants as a meristematic inhibitor. At thegrowth stage that these corn plants were treated, the meristematicregion of the plant is imbedded inside the main stem tissue (in otherwords it is not exposed for direct chemical application). With theresearch methods used in this experiment the only known way theherbicide active ingredient could reach the meristem resulting in plantmortality is absorption through the leaf surface and subsequenttranslocation to the meristematic region.

In this example, all above ground leaf tissue was removed from the cornplants after treatment application (tissue was cut off and removed fromthe plant). This plant harvest technique occurred 30, 60 and 120 minutesafter treatment application. Since absorption and translocation had tooccur while the plant still had sprayed leaf tissue intact, plantcontrol or plant mortality only occurred in those treatments wherebyspeed of absorption was complete within the time frame prior to plantharvest.

Results & Discussion: At 7 days after treatment (DAT) the treatmentscontaining ammonium sulfate as an added adjuvant had herbicide symptomsranging from 0 to 97% control. Detailed data are contained in thefollowing table:

TABLE II % Control of RR Corn 7-DAT at 3 Use Rate Different PlantHarvest Intervals. Product ID** (lb ai/a) 30 minutes 60 minutes 120minutes* Untreated — 0 0 0 Formulation A 0.075 7 43 93 Formulation B0.075 17 13 85 Formulation C 0.075 0 94 97 Formulation D 0.075 0 60 97Prism 0.075 30 28 37 *At the 120 minute plant harvest interval allexperimental clethodim formulations had numerically higher % RR corncontrol than did the commercial standard formulation Prism, indicatingan increased speed of herbicide absorption as a function of these newexperimental formulations. Formulations C and D had 97% control at the120 minute plant harvest interval compared to 37% for Prism. At the 60minute plant harvest interval Formulation C had 94% control. **Alltreatments had ammonium sulfate added at 2.5 lbs product/acre.

Significance: The results of Example 1 demonstrate that the enhancedclethodim formulations of the present invention are superior to PRISM® 1EC, due to increased speed of herbicide absorption, resulting in morerapid herbicide symptoms in susceptible weed species. This Example showsthat the formulations of the present invention also demonstrateincreased speed of herbicide absorption when mixed with ammoniumsulfate.

Example 3

Formulations A and E of the present invention were compared with SELECT®2 EC in their ability to control volunteer ROUNDUP READY® corn when tankmixed with glyphosate without the addition of a crop oil concentrate(COC) adjuvant. The results in Tables IIIA and IIIB show that theformulations of the present invention provide superior control underthese conditions.

Materials & Methods—General Application: ROUNDUP READY® soybeans wereused in these examples with ROUNDUP READY® volunteer corn as the targetgrass species. Application was made to actively growing soybeans andROUNDUP READY® volunteer corn. All herbicide treatments, within a test,were made using identical equipment and application methods.

Results & Discussion: At 1 month after application, the treatmentscontaining Formulations A and E, without the addition of any COCadjuvant, resulted in more complete control compared to Select 2 EC.Detailed data are contained in the following tables:

TABLE IIIA Product ID Glyphosate + Glyphosate + Use Rate (lb ai/a)Formulation A* Select* glyphosate + Untreated 0.75 to 1.0 + 0.75 to1.0 + clethodim — 0.063 0.063 Location Corn Size DAT % Control Purdue —— 0 95 73 University Kansas State 10 to 16″ 30 0 99 48 University AlveyAg 10 to 12″ 29 0 97 53 Research Van Diest, 24 to 28″ 37 0 88 48 Harlan,IA University of 18 to 24″ 12 0 93 73 Illinois Ohio State  9 to 10″ 29 090 65 University Greenville, 12 to 14″ 34 0 92 84 MS Average — — 0.094.4 63.4 *All treatments had ammonium sulfate added at 2.5 lbsproduct/acre.

TABLE IIIB Product ID Use Rate (lb ai/a) Glyphosate + Glyphosate +glyphosate + Untreated Formulation E Select clethodim — 0.78 + 0.0880.78 + 0.094 Location Corn Size DAT % Control Greenville, 18 to 25″ 23 086 15 MS

Significance: Clethodim is known to provide excellent control of a widearray of grassy weeds; however, the effectiveness of clethodim isdependent on the addition of a COC adjuvant, which may not always be adesirable addition to the spray program, and is in fact prohibited onmany glyphosate labels. The enhanced clethodim formulations of thepresent invention provide more complete control of grasses than SELECT®2EC in glyphosate tank mixes without the addition of a COC adjuvant.

Example 4

The control of ROUNDUP READY® corn at 7 and 14 days after treatment(DAT) was compared for the herbicidal formulations of the presentinvention and PRISM® 1 EC. The results presented in Table IV show thatthe formulations of the present invention demonstrate increased speed ofcontrol, resulting in more rapid herbicide symptoms in susceptible weedspecies.

Materials & Methods—General Application: ROUNDUP READY® corn was used inthis example as the target weed species. Applications were made toactively growing corn which had reached 12-18 inches in height. Allherbicide treatments were made using identical equipment and applicationmethods.

Results & Discussion: At 7 and 14 days after treatment (DAT) thetreatments containing Formulations A, B, C, and D resulted in quickerand more complete grass control compared to the commercial PRISM®formulation. Detailed data are contained in the following table:

TABLE IV % Control of RR Corn at 7 and Use Rate 14 Days After TreatmentProduct ID (lb ai/a) 7 DAT 14 DAT Untreated — 0 0 Formulation A 0.07551.7 91.7 Formulation B 0.075 41.7 90.0 Formulation C 0.075 70.0 97.7Formulation D 0.075 55.0 97.0 Prism 0.075 36.7 85.0

Significance: Clethodim is known to provide excellent control of a widearray of grassy weeds, however the speed of visual activity generallyrequires up to 10 days. The clethodim formulations of the presentinvention provide much quicker visual control symptoms than PRISM®,providing the user with an earlier assurance that the product isworking.

Example 5

The control of ROUNDUP READY® corn at 7 and 14 days after treatment(DAT) was compared for the herbicidal formulations of the presentinvention and PRISM® 1 EC, where ammonium sulfate was added to theformulations. Ammonium sulfate is commonly used and often required as atank mix adjuvant with glyphosate to increase efficacy. The resultspresented in Table V show that the formulations of the present inventiondemonstrate increased speed of control under these conditions.

Materials & Methods-General Application: ROUNDUP READY® corn was used inthis example as the target weed species. Applications were made toactively growing corn which had reached 12-18 inches in height. Allherbicide treatments included ammonium sulfate at 2.5 lbs per acre andwere made using identical equipment and application methods.

Results & Discussion: At 7 and 14 days after treatment (DAT) thetreatments containing Formulations A, B, C, and D resulted in quickerand more complete grass control compared to the commercial PRISM®formulation of clethodim. Detailed data are contained in the followingtable:

TABLE V % Control of RR Corn at 7 and Use Rate 14 Days After TreatmentProduct ID* (lb ai/a) 7 DAT 14 DAT Untreated — 0 0 Formulation A 0.07555.0 96.0 Formulation B 0.075 51.7 96.0 Formulation C 0.075 85.0 98.3Formulation D 0.075 88.3 99.3 Prism 0.075 41.7 91.7 *All treatments hadammonium sulfate added at 2.5 lbs product/acre.

Significance: Clethodim is known to provide excellent control of a widearray of grassy weeds, however the speed of visual activity generallyrequires up to 10 days. The clethodim formulations of the presentinvention, with added ammonium sulfate, provide much quicker visualcontrol symptoms than PRISM®, providing the user with an earlierassurance that the product is working.

Example 6

Select 2 EC tank mixed with a nonionic surfactant (NIS) adjuvant andFormulation A of the present invention were compared for their abilityto increase the speed of glyphosate absorption in several weed species.The results in Table VI show that the tank mix of glyphosate withFormulation A increased the speed of glyphosate absorption compared toboth glyphosate alone and glyphosate tank mixed with SELECT® plus a NISadjuvant, resulting in more rapid herbicide symptoms in susceptible weedspecies.

Materials & Methods—General Application: ROUNDUP READY® soybeans wereused in this example as the crop, and indigenous common lambsquarters(Chenopodium album) and giant foxtail (Setaria faben), as well as sowedROUNDUP READY® corn, were used as target weed species. The source of theglyphosate was ROUNDUP WEATHERMAX®, a product of Monsanto. A singleapplication was made to actively growing weeds, which had reached 1 to13 inches in height. All herbicide treatments included ammonium sulfateat 2.5 lbs per acre and were made using identical equipment andapplication methods.

Results & Discussion: At 8 and 14 days after treatment (DAT) thetreatments containing SELECT® 2 EC plus NIS adjuvant and Formulation A,which have no biological activity on broadleaf plants such as commonlambsquarters, both resulted in quicker and in some cases more completeweed control compare˜to the glyphosate treatment applied alone. But theFormulation A treatment was even better than the SELECT® 2 EC treatmentwhich contained an added tank mix adjuvant (NIS). Detailed data arecontained in the following table:

TABLE VI % Weed Control at 8 and 14 DAT common giant RR Use Ratelambsquarters foxtail volunteer corn Product ID* (lb ai/a) 8 DAT 14 DAT8 DAT 14 DAT 8 DAT 14 DAT Untreated — 0 0 0 0 0 0 Roundup 1.00 91.7 93.391.7 97.7 0 0 WeatherMax Roundup 1.00 + 0.078 97.7 97.7 99.0 96.3 73.381.8 WeatherMax + Formulation A Roundup WeatherMax + 1.0 + 0.078 + 96.396.3 97.6 99.9 68.3 81.6 Select + NIS 0.25% v/v *All treatments hadammonium sulfate added at 2.5 lbs product/acre.

Significance: Glyphosate is known for providing slow and effectivecontrol of problem weeds. Efforts to increase the speed of control havehistorically resulted in a decrease in overall control at >14 days aftertreatment (DAT), although the control at <14 DAT may have been have beenincreased. The addition of Formulation A to the glyphosate treatment,which was intended to control volunteer ROUNDUP READY® corn, not onlycontrolled the ROUNDUP READY® corn, but also increased the speed ofcommon lambsquarters and giant foxtail control (8 DAT rating) withoutdecreasing the overall control at 14 DAT compared to glyphosate aloneand glyphosate plus SELECT® 2 EC.

Example 7

Table VII illustrates that the clethodim formulations of the presentinvention are superior to SELECT® 2 EC, even when used at a lower amountof active ingredient per acre, because they can be tank-mixed with otherherbicides without a decrease in grass control.

Materials & Methods—General Application: Peanuts were used in thisexample with Texas panicum (Panicum texanum) as the target weed species.The additional herbicides used were CADRE® (active ingredient imazapic,available from BASF Corporation), STORM™ (active ingredients acifluorfenand bentazone, available from United Phosphorus Incorporated), andCOBRA® (active ingredient lactofen, available from Valent U.S.A.Corporation). Applications were made to actively growing panicum whichhad reached 6 inches in height. All herbicide treatments were made usingidentical equipment and application methods.

Results & Discussion: At 53 days after treatment, the treatmentscontaining Formulation B resulted in no antagonism and superior controlwhen tank-mixed with common broadleaf peanut herbicides that are knownto be antagonistic to clethodim's postemergence grass activity.Formulation B applied at 80% of the dose rate of SELECT® and tank-mixedwith common broadleaf herbicides resulted in weed control superior toSELECT® when tank-mixed with STORM™ and COBRA®, and equal weed controlwhen tank-mixed with CADRE®. Detailed data are contained in thefollowing table:

TABLE VII % Control of Texas Panicum Use Rate at 53 Days After TreatmentProduct (ounces of Select @ 0.125 Formulation B @ 0.10 ID* product/acre)lb ai/a lb ai/a — — 98.0 92.3 Cadre 1.44 95.8 94.5 Storm 24 81.3 93.3Cobra 12.5 83.8 91.0 *All treatments contained COC.

Significance: Clethodim is known to provide excellent control of a widearray of grassy weeds; however, some commonly used postemergencebroadleaf herbicides are known to reduce clethodim's grass activity(antagonism) when tank-mixed with clethodim. The clethodim formulationsof the present invention can be tank-mixed with these broadleafherbicides without a decrease in grass control, even when used at alower amount of active ingredient per acre than the commercial SELECT® 2EC formulation.

Example 8

Table VIII illustrates that the enhanced clethodim formulations of thepresent invention are superior to SELECT® 2 EC, because they do notrequire a crop oil concentrate (COC) adjuvant to provide commerciallyacceptable grass control, unlike current commercial clethodimformulations.

Materials & Methods—General Application: ROUNDUP READY® cotton was usedin this example with barnyardgrass (Echinochloa crus galli) as thetarget grass species. Application was made to actively growing cottonand barnyardgrass which had reached 6-10 inches in height. All herbicidetreatments included ammonium sulfate at 2.5 lbs per acre and were madeusing identical equipment and application methods.

Results & Discussion: At 7 and 33 days after treatment (DAT) thetreatments containing Formulations A and B without the addition of a COCadjuvant resulted in quicker and more complete grass control compared tothe commercial SELECT® 2 E˜formulation. Detailed data are contained inthe following table:

TABLE VIII % Control of Barnyardgrass at 7 and 33 Days After TreatmentUse Rate 7 DAT 33 DAT Product ID* (lb ai/a) −COC +COC −COC +COCUntreated — 0 0 0 0 Formulation A 0.094 73.3 70.0 96.0 96.7 FormulationB 0.094 70.0 73.3 97.0 97.7 Select 2 EC 0.094 41.7 70.0 46.7 84.0 *Alltreatments had ammonium sulfate added at 2.5 lbs product/acre.

Significance of Invention: Clethodim is known to provide excellentcontrol of a wide array of grassy weeds. However, the effectiveness ofclethodim has thus far been dependent on the addition of a COC adjuvant,which may not always be a desirable addition to the spray program. Theenhanced clethodim formulations of the present invention provide fasterand more complete control without the addition of a COC.

Example 9

Several formulations of the present invention were tested for chemicalstability along with a comparative clethodim formulation containingC16-C18 fatty acid methyl esters. Table IX illustrates that the enhancedclethodim formulations of the present invention are storage stable forextended periods and have improved chemical stability compared to asimilar formulation not of the present invention.

Materials and Methods: Several formulations were tested for stability ofthe active ingredient over various time periods at 40° C. or at roomtemperature. The percent clethodim remaining was calculated based on astarting clethodim value of 100%.

Results and Discussion: The chemical stability results are indicated inthe following Table IX. The chemical stability of formulationscontaining clethodim is an important consideration, since many standardadjuvant materials and surfactants, including calcium DDBS, are known inthe art to cause rapid degradation of clethodim and othercyclohexanedione oximes. Yet the results show that these formulationsare unexpectedly stable over extended periods of time.

TABLE IX % Clethodim Remaining Storage Storage Time Product IDTemperature. 2 months 6 months 12 months Formulation A 40° C. 95.9 — —room temp. — 97.5 — Formulation B 40° C. 95.4 — — room temp. — 98.0 —Formulation C room temp. — 93.6 — Formulation D room temp. — 93.9 —Formulation F 40° C. 92.9 — — room temp. — 98.4 95.2 Formulation G 40°C. 92.9 — — room temp. — 97.5 94.0 Formulation H 40° C. 91.7 — — roomtemp. — 99.6 93.2 Formulation I* room temp. — 87.9 — *Formulation I wastested for comparison purposes and is not a formulation of the presentinvention.

Significance: Addition of many types of adjuvant materials andsurfactants, including calcium DDBS, to formulations of clethodim andother cyclohexanedione oximes can cause rapid degradation of the activeingredient. The formulations of the present invention containsignificant amounts of a fatty acid methyl ester adjuvant and calciumDDBS and yet are chemically stable over extended periods of time. Theyalso show improved chemical stability over a formulation not of thepresent invention which also contains a fatty acid methyl esteradjuvant.

1. An herbicidal composition comprising: (a) an effective amount of anherbicidal cyclohexanedione oxime compound or agriculturally acceptablesalt thereof; (b) one or more esters of a fatty acid; (c) a salt ofdodecylbenzenesulfonic acid; and (d) at least one nonionic surfactantselected from the group consisting of polyoxyethylene plant oils andpolyoxyethylene sorbitan esters wherein the nonionic surfactant has ahydrophilic-lipophilic balance (HLB) value of about 14.4-18.0; with theproviso that the composition does not include additional phenylpyrazolesafeners.
 2. The herbicidal composition of claim 1 wherein saidherbicidal cyclohexanedione oxime compound is clethodim, sethoxydim,alloxydim, cycloxydim, butroxydim, tralkoxydim, tepraloxydim, orprofoxydim.
 3. The herbicidal composition of claim 1 wherein saidherbicidal cyclohexanedione oxime compound is clethodim or sethoxydim.4. The herbicidal composition of claim 1 wherein said herbicidalcyclohexanedione oxime compound is clethodim.
 5. The herbicidalcomposition of claim 1 that contains 3 to 30% by weight of saidherbicidal cyclohexanedione oxime compound or agriculturally acceptablesalt thereof.
 6. The herbicidal composition of claim 1 wherein saidesters of a fatty acid are C1-C8 alkyl esters of C12-C22 organicmonobasic acids.
 7. The herbicidal composition of claim 1 wherein saidesters of a fatty acid are methyl oleate, methyl palmitate, isopropylmyristate, octyl laurate, isopropyl palmitate, butyl stearate, ormixtures thereof.
 8. The herbicidal composition of claim 1 that contains0.5 to 8% of said nonionic surfactant.
 9. The herbicidal composition ofclaim 1 that contains 0.5 to 5% of said salt of dodecylbenzenesulfonicacid.
 10. An herbicidal composition of claim 1 that includes at leastone additional herbicide.
 11. An herbicidal composition of claim 10where the at least one additional herbicide is selected from glyphosate,lactofen, imazapic, acifluorfen, bentazone and/or pyrithiobac-sodium.12. An herbicidal composition of claim 11 where the additional herbicideis glyphosate.
 13. An herbicidal composition of claim 11 where theadditional herbicide is lactofen.
 14. An herbicidal composition of claim11 where the additional herbicide is imazapic.
 15. An herbicidalcomposition of claim 11 where the additional herbicide is acifluorfen.16. An herbicidal composition of claim 11 where the additional herbicideis bentazone
 17. An herbicidal composition of claim 11 where theadditional herbicide is pyrithiobac-sodium.
 18. The herbicidalcomposition of claim 1 or 10 that comprises one or more additionalsolvents.
 19. The herbicidal composition of claim 1 or 10 wherein saidadditional solvents are selected from the group consisting of2-ethylhexanol, propylene glycol, ethylene glycol, diethylene glycol,and glycerin.